Competitive Adsorption of Chloroform and Iron Ion onto Activated Carbon Fiber

Chloroform in tap water has been a significant problem because it may be a carcinogenic substituent. Iron ion exists in tap water because of dissolution from iron water pipes. Iron ions in tap water cause discoloration and a bad odor. The isotherms of chloroform and iron ion adsorption onto activated carbon fibers in a single solution (chloroform or iron ion) and in a binary mixture solution (chloroform and iron ion) were investigated to estimate the competitiveness between chloroform and iron ions. The amount of adsorbed iron ions increased with increasing pore volume of the activated carbon fibers, while that of chloroform decreased. The amount of chloroform adsorbed onto the activated carbon fibers in the binary mixture solution was greater than that in the single solution. These results indicate that the adsorption of chloroform and iron ion onto activated carbon fibers could be competitive.     

Structural characteristics of activated carbons and ibuprofen adsorption affected by bovine serum albumin

Structural characteristics of a series of MAST carbons were studied using scanning electron microscopy images and the nitrogen adsorption isotherms analyzed with several models of pores and different adsorption equations. A developed model of pores as a mixture of gaps between spherical nanoparticles and slitlike pores was found appropriate for MAST carbons. Adsorption of ibuprofen [2-(4-isobutylphenyl)propionic acid] on activated carbons possessing different pore size distributions in protein-free and bovine serum albumin (BSA)-containing aqueous solutions reveals the importance of the contribution of mesopores to the total porosity of adsorbents. The influence of the mesoporosity increases when considering the removal of the drug from the protein-containing solution. Cellulose-coated microporous carbon Norit RBX adsorbs significantly smaller amounts of ibuprofen than uncoated micro/mesoporous MAST carbons whose adsorption capability increases with increasing mesoporosity and specific surface area, burnoff dependent variable. A similar effect of broad pores is observed on adsorption of fibrinogen on the same carbons. Analysis of the ibuprofen adsorption data using Langmuir and D'Arcy-Watt equations as the kernel of the Fredholm integral equation shows that the nonuniformity of ibuprofen adsorption complexes diminishes with the presence of BSA. This effect may be explained by a partial adsorption of ibuprofen onto protein molecules immobilized on carbon particles and blocking of a portion of narrow pores.     

Pore structure and adsorption performance of the KOH-activated carbons prepared from corncob

Carbonaceous adsorbents with controllable surface area were chemically activated with KOH at 780 degrees C from chars that were carbonized from corncobs at 450 degrees C. The pore properties, including BET surface area, pore volume, pore size distribution, and mean pore diameter of these activated carbons, were characterized by the t-plot method based on N(2) adsorption isotherms. Two groups are classified according to the types of adsorption/desorption isotherms. Group I corncob-derived activated carbons, with KOH/char ratios from 0.5 to 2, exhibited BET surface area ranging from 841 to 1221 m(2)/g. Group II corncob-derived activated carbons, with KOH/char rations from 3 to 6, showed high BET surface areas, from 1976 to 2595 m(2)/g. From scanning electron microscopic (SEM) results, the surface morphology of honeycombed holes on corncob-derived activated carbons was significantly influenced by the KOH/char ratios. The adsorption kinetics of methylene blue, basic brown 1, acid blue 74, 2,4-dichlorophenol, 4-chlorophenol, and phenol from water at 30 degrees C were studied on the two groups of activated carbons, which were suitably described by two simplified kinetic models, pseudo-first-order and pseudo-second-order equations. The effective particle diffusivities of phenols and dyes at the corncob-derived activated carbons of group II are higher than those of ordinary activated carbons. The high-surface-area activated carbons were demonstrated to be promising adsorbents for pollution control and for other applications.     

Preparation of highly porous carbon from fir wood by KOH etching and CO2 gasification for adsorption of dyes and phenols from water

Fir wood was first carbonized for 1.5 h at 450 degrees C, then soaked in a KOH solution KOH/char ratio of 1, and last activated for 1 h at 780 degrees C. During the last hour CO2 was poured in for further activation for 0, 15, 30, and 60 min, respectively. Carbonaceous adsorbents with controllable surface area and pore structure were chemically activated from carbonized fir wood (i.e., char) by KOH etching and CO2 gasification. The pore properties, including the BET surface area, pore volume, pore size distribution, and pore diameter, of these activated carbons were first characterized by the t-plot method based on N2 adsorption isotherms. Fir-wood carbon activated with CO2 gasification from 0 to 60 min exhibited a BET surface area ranging from 1371 to 2821 m2 g(-1), with a pore volume significantly increased from 0.81 to 1.73 m2 g(-1). Scanning electron microscopic (SEM) results showed that the surfaces of honeycombed holes in these carbons were significantly different from those of carbons without CO2 gasification. The adsorption of methylene blue, basic brown 1, acid blue 74, p-nitrophenol, p-chlorophenol, p-cresol, and phenol from water on all the carbons studied was examined to check their chemical characteristics. Adsorption kinetics was in agreement with the Elovich equation, and all equilibrium isotherms were in agreement with the Langmuir equation. These results were used to compare the Elovich parameter (1/b) and the adsorption quantity of the unit area (q(mon)/Sp) of activated carbons with different CO2 gasification durations. This work facilitated the preparation of activated carbon by effectively controlling pore structures and the adsorption performance of the activated carbon on adsorbates of different molecular forms.     

Carbon slit pore model incorporating surface energetical heterogeneity and geometrical corrugation

In our recent paper (Jagiello and Olivier, Carbon 55:70–80, 2013) we considered introducing energetical heterogeneity (EH) and geometrical corrugation (GC) to the pore walls of the standard carbon slit pore model. We treated these two effects independently and we found that each of them provides significant improvement to the carbon model. The present work is a continuation of the previous one, as we include both effects in one comprehensive model. The existing standard slit pore model widely used for the characterization of activated carbons assumes graphite-like energetically uniform pore walls. As a result of this assumption adsorption isotherms calculated by the non-local density functional theory (NLDFT) do not fit accurately the experimental N₂ data measured for real activated carbons. Assuming a graphene-based structure for activated carbons and using a two-dimensional-NLDFT treatment of the fluid density in the pores we present energetically heterogeneous and geometrically corrugated (EH–GC) surface model for carbon pores. Some parameters of the model were obtained by fitting the model to the reference adsorption data for non-graphitized carbon black. For testing, we applied the new model to the pore size analysis of porous carbons that had given poor results when analyzed using the standard slit pore model. We obtained an excellent fit of the new model to the experimental data and we found that the typical artifacts of the standard model were eliminated.     

Comparisons of porous and adsorption properties of carbons activated by steam and KOH

In this work, fir woods and pistachio shells were used as source materials to prepare porous carbons, which were activated by physical (steam) and chemical (KOH) methods. Pore properties of these activated carbons including the BET surface area, pore volume, pore size distribution, and pore diameter were first characterized by a t-plot method based on N(2) adsorption isotherms. Highly porous activated carbons with BET surface area up to 1009-1096 m(2)/g were obtained. The steam and KOH activation methods produced carbons with mesopore content in the range 9-15 and 33-49%, respectively. The adsorption equilibria and kinetics of tannic acid, methylene blue, 4-chlorophenol, and phenol from water on such carbons at 30 degrees C were then investigated to check their chemical characteristics. The Freundlich equation gave a better fit to all adsorption isotherms than the Langmuir equation. On the other hand, the intraparticle diffusion model could best follow all adsorption processes. In comparison with KOH-activated carbons, it was shown that the rate of external surface adsorption with steam-activated carbons was significantly higher but the rate of intraparticle diffusion was much lower.     

Adsorption of Carbon Dioxide on Activated Carbon

The adsorption of CO2 on a raw activated carbon A and three modified activated carbon samples B, C, and D at temperatures ranging from 303 to 333 K and the thermodynamics of adsorption have been investigated using a vacuum adsorption apparatus in order to obtain more information about the effect of CO2 on removal of organic sulfur-containing compounds in industrial gases. The active ingredients impregnated in the carbon samples show significant influence on the adsorption for CO2 and its volumes adsorbed on modified carbon samples B, C, and D are all larger than that on the raw carbon sample A. On the other hand, the physical parameters such as surface area, pore volume, and micropore volume of carbon samples show no influence on the adsorbed amount of CO2. The Dubinin-Radushkevich (D-R) equation was the best model for fitting the adsorption data on carbon samples A and B, while the Preundlich equation was the best fit for the adsorption on carbon samples C and D. The isosteric heats of adsorption on carbon samples A, B, C, and D derived from the adsorption isotherms using the Clapeyron equation decreased slightly increasing surface loading. The heat of adsorption lay between 10.5 and 28.4 kJ/mol, with the carbon sample D having the highest value at all surface coverages that were studied. The observed entropy change associated with the adsorption for the carbon samples A, B, and C (above the surface coverage of 7 ml/g) was lower than the theoretical value for mobile adsorption. However, it was higher than the theoretical value for mobile adsorption but lower than the theoretical value for localized adsorption for carbon sample D.     

The physical and surface chemical characteristics of activated carbons and the adsorption of methylene blue from wastewater

Adsorption of a basic dye, methylene blue, from aqueous solutions onto as-received activated carbons and acid-treated carbons was investigated. The physical and surface chemical properties of the activated carbons were characterized using BET-N(2) adsorption, X-ray photoelectron spectroscopy (XPS), and mass titration. It was found that acid treatment had little effect on carbon textural characteristics but significantly changed the surface chemical properties, resulting in an adverse effect on dye adsorption. The physical properties of activated carbon, such as surface area and pore volume, have little effect on dye adsorption, while the pore size distribution and the surface chemical characteristics play important roles in dye adsorption. The pH value of the solution also influences the adsorption capacity significantly. For methylene blue, a higher pH of solution favors the adsorption capacity. The kinetic adsorption of methylene blue on all carbons follows a pseudo-second-order equation.     

Adsorption of NOM onto Activated Carbon: Effect of Surface Charge, Ionic Strength, and Pore Volume Distribution

Adsorption of natural organic matter (NOM) onto seven activated carbons with a wide range of surface properties was studied at high and low ionic strength over a range of pH values. From adsorption isotherm studies it was found that, for six of seven carbons, at low surface concentrations, increased ionic strength decreased NOM adsorption. As the surface concentration increased, the adsorption isotherms converged and intersected, after which the addition of salt resulted in increased adsorption. This “crossover point” marked a change in the adsorption mechanism from the “screening reduced” to the “screening enhanced” adsorption regimes. The adsorption mechanisms are extremely complicated and appear attributable to various factors, including electrostatic forces, pore volume distribution, and chemical interactions between the NOM and the surface functionalities on the carbon surfaces.     

Study of chromium(VI) adsorption onto modified activated carbons with respect to analytical application

Two different types of modification of activated carbon, by treatment with concentrated solution of HNO₃ and outgassing treatment at high temperature, were studied in order to obtain the most effective adsorption of chromium(VI) ions from water solution. The basic parameters affecting the adsorption capacity of Cr(VI) ions on modified activated carbons were studied in details and the effect of modifications of activated carbons has been determined by studying the initial runs of adsorption isotherms. The obtained Cr(VI) adsorption isotherms were well fitted in the Freundlich equation. The reduction of Cr(VI) to Cr(III) and further ion exchange mechanism of adsorption onto oxidizing activated carbon and surface precipitation to Cr(OH)₃ in case of outgassing activated carbon were found as the main adsorption mechanisms of Cr(VI) ions onto modified activated carbons. Presence of chlorides and nitrates in studied adsorption system strongly decreased the adsorption ability of Cr(VI) onto outgassing activated carbon and mechanism of this behavior is proposed.     

Potassium bromate modification of the granular activated carbon and its effect on nickel adsorption

Granular Activated Carbon (GAC), a commercial adsorbent for the removal of heavy metals was treated chemically with potassium bromate for it’s surface modification and it’s adsorption capacity was investigated with nickel ions. There was an increase in the adsorption capacity of the modified carbon by 90–95% in comparison to the raw granular activated carbon towards nickel ion adsorption. Potassium Bromate oxidation treatment was employed for a period of about 30 mins initially followed by 60 mins and the oxidized carbons were adsorbed with nickel ions. Metal sorption characteristics of as received and modified activated carbons were measured in batch experiments. Batch adsorption was successfully modeled by Langmuir Isotherm Model which indicates monolayer adsorption. The adsorption isotherms also fit well to the Freundlich Model. Effects of pH of initial solution, time of oxidation and mode of treatment on the adsorption process were studied. Experimental results showed that metal uptake increased with an increase in pH and oxidation time. The samples were characterized by Scanning Electron Microscope (SEM) studies and surface area analyzer.     

Hydrogen adsorption in transition metal carbon nano-structures

Templated microporous carbons were synthesized from metal impregnated zeolite Y templates. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were employed to characterize morphology and structure of the generated carbon materials. The surface area, micro- and meso-pore volumes, as well as the pore size distribution of all the carbon materials were determined by N₂ adsorption at 77 K and correlated to their hydrogen storage capacity. All the hydrogen adsorption isotherms were Type 1 and reversible, indicating physisorption at 77 K. Most templated carbons show good hydrogen storage with the best sample Rh-C having surface area 1817 m²/g and micropore volume 1.04 cm³/g, achieving the highest as 8.8 mmol/g hydrogen storage capacity at 77 K, 1 bar. Comparison between activated carbons and synthesized templated carbons revealed that the hydrogen adsorption in the latter carbon samples occurs mainly by pore filling and smaller pores of sizes around 6 Å to 8 Å are filled initially, followed by larger micropores. Overall, hydrogen adsorption was found to be dependent on the micropore volume as well as the pore-size, larger micropore volumes showing higher hydrogen adsorption capacity.     

Adsorption of NH3 onto activated carbon prepared from palm shells impregnated with H2SO4

Adsorption of ammonia (NH3) onto activated carbons prepared from palm shells impregnated with sulfuric acid (H2SO4) was investigated. The effects of activation temperature and acid concentration on pore surface area development were studied. The relatively large micropore surface areas of the palm-shell activated carbons prepared by H2SO4 activation suggest their potential applications in gas adsorption. Adsorption experiments at a fixed temperature showed that the amounts of NH3 adsorbed onto the chemically activated carbons, unlike those prepared by CO2 thermal activation, were not solely dependent on the specific pore surface areas of the adsorbents. Further adsorption tests for a wide range of temperatures suggested combined physisorption and chemisorption of NH3. Desorption tests at the same temperature as adsorption and at an elevated temperature were carried out to confirm the occurrence of chemisorption due to the interaction between NH3 and some oxygen functional groups via hydrogen bonding. The surface functional groups on the adsorbent surface were detected by Fourier transform infrared spectroscopy. The amounts of NH3 adsorbed by chemisorption were correlated with the contents of elemental oxygen present in the adsorbents. Mechanisms for chemical activation and adsorption processes are proposed based on the observed phenomena.     

Storage of hydrogen at 303 K in graphite slitlike pores from grand canonical Monte Carlo simulation

Grand canonical Monte Carlo (GCMC) simulations were used for the modeling of the hydrogen adsorption in idealized graphite slitlike pores. In all simulations, quantum effects were included through the Feynman and Hibbs second-order effective potential. The simulated surface excess isotherms of hydrogen were used for the determination of the total hydrogen storage, density of hydrogen in graphite slitlike pores, distribution of pore sizes and volumes, enthalpy of adsorption per mole, total surface area, total pore volume, and average pore size of pitch-based activated carbon fibers. Combining experimental results with simulations reveals that the density of hydrogen in graphite slitlike pores at 303 K does not exceed 0.014 g/cm(3), that is, 21% of the liquid-hydrogen density at the triple point. The optimal pore size for the storage of hydrogen at 303 K in the considered pore geometry depends on the pressure of storage. For lower storage pressures, p < 30MPa, the optimal pore width is equal to a 2.2 collision diameter of hydrogen (i.e., 0.65 nm), whereas, for p congruent with 50MPa, the pore width is equal to an approximately 7.2 collision diameter of hydrogen (i.e., 2.13 nm). For the wider pores, that is, the pore width exceeds a 7.2 collision diameter of hydrogen, the surface excess of hydrogen adsorption is constant. The importance of quantum effects is recognized in narrow graphite slitlike pores in the whole range of the hydrogen pressure as well as in wider ones at high pressures of bulk hydrogen. The enthalpies of adsorption per mole for the considered carbonaceous materials are practically constant with hydrogen loading and vary within the narrow range q(st) congruent with 7.28-7.85 kJ/mol. Our systematic study of hydrogen adsorption at 303 K in graphite slitlike pores gives deep insight into the timely problem of hydrogen storage as the most promising source of clean energy. The calculated maximum storage of hydrogen is equal to approximately 1.4 wt %, which is far from the United States Department of Energy (DOE) target (i.e., 6.5 wt %), thus concluding that the total storage amount of hydrogen obtained at 303 K in graphite slitlike pores of carbon fibers is not sufficient yet.     

Multicomponent Adsorption of Pesticides onto Activated Carbon Fibers

The adsorption equilibria of pesticides and metabolites (atrazine, deethylatrazine, deisopropylatrazine and simazine) are studied onto activated carbon fibers –ACF– with a broad pore size distribution (32% mesopore volume, 68% micropore volume). Mono-and multi-component isotherms have been determined for low concentrations, from 0.23×10⁻⁶ to 9.52×10⁻⁶ mol L⁻¹. Single solute isotherms, modeled by Freundlich and Langmuir models, tend to prove the influence of the adsorbate's solubility in the adsorption capacity of activated carbon fibers. Binary solute isotherms confirm the strong influence of pesticide solubility on the competitive adsorption mechanism: the competition is higher in the case of adsorbates of different solubilities (atrazine and DEA or DIA for example). Multicomponent experimental data were modeled by extended Langmuir-based equations and the Ideal Adsorbed Solution theory. Whereas the first ones failed to model accurately binary adsorption due to restrictive hypothesis, the IAS model showed a good agreement between experimental and predicted data. It emphasised also the difficulty in satisfying the hypothesis of the model in the case of highly adsorbed compounds. Finally, the simultaneous adsorption of atrazine and NOM (in a natural water, DOC = 18.2 mg L⁻¹) shows no adsorption competition effects between natural organic matter and atrazine. This is due to the presence of secondary micropores (0.8–2 nm) and mesopores in the ACF, which limit a pore blockage phenomenon by NOM.     

Micropore Filling of Supercritical Xe in Micropores of Activated Carbon Fibers

The adsorption isotherms of Xe vapor at 196 K and supercritical Xe at 300 K on activated carbon fibers of different pore widths were gravimetrically measured. The adsorption isotherms of Xe vapor were compared with the N(2) adsorption isotherms. A Dubinin-Radushkevich (DR) plot of the adsorption isotherms of Xe vapor showed a good linearity, indicating that Xe vapor is adsorbed by the representative micropore filling mechanism. The adsorption isotherms of supercritical Xe were approximated by the Langmuir equation. The saturated adsorption amounts of supercritical Xe, W(L), were in the range of 0.14 to 0.22 ml g(-1). The adsorption isotherms of supercritical Xe were described by the supercritical DR equation, which provides the quasisaturated vapor pressure P(0q). Both P(0q) and W(L) lead to the reduced isotherm, which can describe three isotherms. The obtained reduced isotherm derived from the isotherms of supercritical Xe could describe even those of Xe vapor. Hence, both Xe vapor and supercritical Xe should be adsorbed by the same mechanism. The isosteric heat of Xe adsorption was greater than the enthalpy of vaporization of Xe by more than 12 kJ mol(-1). These results suggest that Xe molecules are stabilized in the form of a cluster in micropores even at 300 K. Copyright 2000 Academic Press.     

Influence of mesoporosity on the sorption of 2,4-dichlorophenoxyacetic acid onto alumina and silica

Two SiO2 and three Al2O3 adsorbents with varying degrees of mesoporosity (pore diameter 2-50 nm) were reacted with 2,4-dichlorophenoxyacetic acid (2,4-D) at pH 6 to investigate the effects of intraparticle mesopores on adsorption/desorption. Anionic 2,4-D did not adsorb onto either SiO2 solid, presumably because of electrostatic repulsion, but it did adsorb onto positively charged Al2O3 adsorbents, resulting in concave isotherms. The Al2O3 adsorbent of highest mesoporosity consistently adsorbed more 2,4-D per unit surface area than did the nonporous and less mesoporous Al2O3 adsorbents over a range of initial 2,4-D solution concentrations (0.025-2.5 mM) and reaction times (30 min-55 d). Differences in adsorption efficiency were observed despite equivalent surface site densities on the three Al2O3 adsorbents. Hysteresis between the adsorption/desorption isotherms was not observed, indicating that adsorption is reversible. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy studies confirm that 2,4-D adsorption does not occur via ligand exchange, but rather via electrostatic interaction. The results indicate that adsorbent intraparticle mesopores can result in consistently greater 2,4-D adsorption, but the amount adsorbed is dependent upon surface charge and the presence of adsorbent mesoporosity. The data also suggest that when mineral pores are significantly larger than the adsorbate, they do not contribute to diffusion-limited adsorption/desorption hysteresis. Adsorbent transformations through time are discussed.     

Cadmium ion adsorption on different carbon adsorbents from aqueous solutions. Effect of surface chemistry, pore texture, ionic strength, and dissolved natural organic matter

Adsorption of Cd(II) species at pH = 5 was studied on three carbon adsorbents: granular activated carbon, activated carbon fiber, and activated carbon cloth. As-received and oxidized adsorbents were used. Cd(II) adsorption greatly increased after oxidation due to the introduction of carboxyl groups. The use of a buffer solution to control the pH introduced some changes in the surface chemistry of carbons through the adsorption of one of the compounds used, biphthalate anions. The increase in ionic strength reduced Cd(II) uptake on both as-received and oxidized carbons due to a screening of the electrostatic attractions between the Cd(II) positive species and the negative surface charge, which in the case of as-received carbons derived from the biphthalate anions adsorbed and in the oxidized ones from the carboxyl groups. Tannic acid was used as a model compound for natural organic matter. Its adsorption was greatly reduced after oxidation, and most of the carbon adsorbents preadsorbed with tannic acid showed an increase in Cd(II) uptake. In the case of competitive adsorption between Cd(II) species and tannic acid molecules, there was a decrease in Cd(II) uptake on the as-received carbon whereas the contrary occurred with the oxidized carbons. These results illustrate the great importance of carbon surface chemistry in this competitive adsorption process. Finally, under all experimental conditions used, when the adsorption capacity of carbons was compared under the same conditions it increased in the following order: granular activated carbon < activated carbon fiber < activated carbon cloth.     

Adsorption of tetraalkylammonium ions on microporous and mesoporous activated carbons prepared from vinylidene chloride copolymer

The adsorption of tetraalkylammonium ions on microporous (AC-micro) and mesoporous (AC-meso) activated carbons prepared from vinylidene chloride copolymer was investigated. The adsorbed amounts on AC-micro decreased in the order of tetraethyl-, tetrapropyl-, hexadecyltrimetyl-, and tetrahexylammonium bromide. Consequently it is suggested that the pore size of the activated carbon plays an important role in the adsorption. The adsorbed amounts on AC-meso increased with increasing alkyl chain length. In the case of mesoporous activated carbon, hydrophobic interaction between tetraalkylammonium ions and the surface of activated carbons contributes to in the adsorption.     

Cluster-Mediated Water Adsorption on Carbon Nanopores

The adsorption isotherms of water at 303 K and N2 at 77 K on various kinds of porous carbons were compared with each other. The saturated amounts of water adsorbed on carbons almost coincided with amounts of N2 adsorption in micropores. Although carbon aerogel samples have mesopores of the great pore volume, the saturated amount of adsorbed water was close to the micropore volume which is much small than the mesopore volume. These adsorption data on carbon aerogels indicated that the water molecules are not adsorbed in mesopores, but in micropores only. The adsorption isotherms of water on activated carbon having micropores of smaller than 0.7 nm in width had no clear adsorption hysteresis, while the water adsorption isotherms on micropores of greater than 0.7 nm had a remarkable adsorption hysteresis above P/P0 = 0.5. The disappearance of the clear hysteresis for smaller micropores suggested that the cluster of water molecules of about 0.7 nm in size gives rise to the water adsorption on the hydrophobic micropores; the formation and the structure of clusters of water molecules were associated with the adsorption mechanism. The cluster-mediated pore filling mechanism was proposed with a special relevance to the evidence on the formation of the ordered water molecular assembly in the carbon micropores by in situ X-ray diffraction.